Alkyl aromatic compounds



Patented Jan. 22, 1946 ALKYL AROMATIC COMPOUNDS Lawrence H. Flett,Hamburg, N. Y., assignor to Allied Chemical & Dye Corporation, acorporation of New York No Drawing. Application June 28, 1941, SerialNo. 400,335

6 Claims. (or. 260-505) This invention relates to new types of productsand to methods for preparing them. It relates more particularly to newtypes of alkylated aromatic compounds and methods for their manufacture.

Alkylated aromatic compounds, having as substituents in the aromaticnucleus, introduced by alkylation, monovalent hydrocarbon radicalsderived from a petroleum distillate (including aliphatic, cycloaliphaticand aralkyl hydrocarbon radicals) have heretofore been produced. Thus.sulfonated compounds of this type have been produced for use asdetergents and surface-active agents.

One process for the manufacture of these products involves chlorinatinga hydrocarbon mixture of the type of a petroleum distillate,

preferably a parafilnic petroleum hydrocarbon distillate; condensingresulting chlorinated hydrocarbons with an aromatic compound with theaid of a condensation catalyst of the Friedel- Crafts type, such asanhydrous aluminum chloride or anhydrous zinc chloride, to form amixture containing alkylated aromatic compounds having as substituentsin the aromatic nucleus, introduced by alkylation, monovalenthydrocarbon radicals sulfonating resulting mixed alkylated aromaticcompounds; and recovering the resulting mixed sulfonic acids, preferablyin the form of their salts, such as their salts with alkali metals.

It is obvious that in order to produce superior products of the abovetype it is important to make certain that the hydrocarbon groupsintroduced by alkylation are of the desired character. It is alsoimportant, if the object is to prepare products adapted for general use,to obtain the mixed alkylated aromatic sulfonates substantially freefrom the hydrocarbon mixture (e. g., the kerosene or white oil fraction)used in manufacturing the products. 7

In the manufacture of mixed alkylated arcmatic sulfonates having thedesired type of hydrocarbon substituent and therefore having desirableproperties, the manner in which the chlo-. rination of the hydrocarbonmixture is carried out is important. References in the literaturedisclose that when chlorinating a hydrocarbon mixture for the purpose offinally replacing a hydrogen atom of the hydrocarbon molecules with someother radical such as the hydroxyl group, the desired products areobtained in the best yields when, at the end of thechlorinationreaction, the amount of organically combined chlorine in the chlorinatedhydrocarbon mixture is obtain from the mixture radicals of thehydrocarbon molecules, it has been considered that the useful productsare obtained substantially entirely from the monochlorinated molecules.The polychlorinated molecules were regarded as undesired impuritieswhich led to the formation of unwanted by-products and whose productionwas to be avoided. It is known that the first chlorine atom introducedintoa hydrocarbon molecule at least does not seriously retard theintroduction of further chlorine atoms into this molecule. For thisreason, as chlorination is continued up to and beyond the point whichcorresponds to the introduction of one chlorine atom for each moleculeof hydrocarbons, it was to be expected that a large proportion of thehydrocarbons present in the mixture would be converted into undesirablepolychlorides. Thus, it was to be expected that while at first, say atthe point where the chlorine which has become combined organically inthe mixture corresponds to about one-fifth of the amount of chlorinewhich would be so combined if each molecule of hydrocarbon in themixture were converted to a monochlor hydrocarbon, the chlorinatedhydrocarbons in the mixture would be predominantly monochlorides, as thechlorination proceeded a proportion of these monochlorides would beconverted into polychlorides. Although it would be expected thatcontinued chlorination would convert some of the unchlorinatedhydrocarbons to the desired monochlorides, it would be expected thatthis action would be accompanied by the conversion of the monochloridesfirst formed into the undesired polychlorides, resulting in a finalmixture containing a high proportion of the polychlorides. On condensingthe mixture containing the polychlorides with an aromatic compound, itwould be expected that the condensation taking place between thepolychlorides and the aromatic compound would defeat the securing ofdesirable hydrocarbon substituted aromatic sulfonates upon the eventualsulfonation of the condensation products.

. As is pointed out in my application Serial No. 329,830, filed April15, 1940, now U. S. Patent 2,247,365, issued July 1, 1941, of which thisappliparafllnic petroleum hydrocarbon distillate, to

such an extent that the amount of chlorine which has become combinedorganically in the mixture is more than that which would be so combinedif each hydrocarbon molecule present in the mixture were converted toits corresponding monochloride, that a chlorinated mixture is obtainedwhich can be used successfull for the production of desired mixedhydrocarbon-substituted aromatic sulfonates with exceptionalsurfaceactive properties. Hereinafter a chlorinated mixture containingan amount of organically combined chlorine which exceeds that whichwould be present if the mixture consisted of monochlorinatedhydrocarbons only is said to be overchlorinated. It has further beenfound that by using an overchlorinated hydrocarbon mixture not only isit possible to obtain desirable mixed hydrocarbon-substituted aromaticsulfonates, but these sulfonates are obtainable in greater yields, basedon the amount of hydrocarbon mixture employed, than when anunderchlorinated hydrocarbon mixture is used. Further, it has beendetermined that the polychlorinated hydrocarbon constituents are notundesirable but condense with the aromatic compound to producehydrocarbon-substituted aromatic compounds in which two non-aromaticcarbon atoms of a hydrocarbon radical introduced by alkylation arelinked directly to two adjacent carbon atoms of the aromatic nucleus.Thus, it has been determined that when a hydrocarbon mixture of the typeof a petroleum distillate is chlorinated to a degree which may be saidto correspond to "more than 100 per cent chlorination and preferably notmore than 200 per cent chlorination" and the resulting chlorinatedhydrocarbon mixture is condensed with an aromatic compound, preferably amononuclear aromatic compound, and especlally benzene, mixtures ofhydrocarbon-substituted aromatic compounds are produced which include,in addition to hydrocarbon-substituted aromatic compounds in which asingle nonarmatic carbon atom of a hydrocarbon radical is linkeddirectly to a carbon atom of the aromatic nucleus,hydrocarbon-substituted aromatic compounds in which two non-aromaticcarbon atoms of a hydrocarbon radical introduced by alkylation arelinked directly to two adjacent carbon atoms of the aromatic nucleus(termed for convenience fcyclo-alkylene-aromatic compounds) and thatwhen such mixtures are sulfonated cyclo-alkylene-aromatic sulfonates areformed which contribute greatly to the surface-active properties of themixtures. Throughout this specification and the claims, per centchlorination is on a molar basis; it refers to the per cent ratiobetween the actual increase in weight due to chlorination of an amountof hydrocarbon distillate corresponding to the average molecular weightof the hydrocarbons in the distillate and the expected increase inweight of the same amount and kind of hydrocarbon distillate if everyhydrocarbon in the amount of hydrocarbon distillate were converted toits corresponding monochlor hydrocarbon; Thus, the per cent chlorinationmay be expressed by the formula:

where 34.5 represents the increase in weight of an average molarquantity of hydrocarbon mixture if all the hydrocarbons in this quantityof mixture were converted to monochlor hydrocarbons only and Irepresents the actual increase in weight of an average molar quantity ofhydrocarbon mixture due to chlorine which is caused to becomeorganically combined in the hydrocarbons of the quantity of mixture bythe chlorination.

In contrast to the prior art which has emphasized the importance ofmaking detergents oi the alkylated aromatic sulfonate type fromchlorinated hydrocarbons which have been chlorinated to a lesser degreethan 100 per cent chlorination, specifically with the object ofobtaining only monochlor hydrocarbons, I have found that high qualitydetergents of the alkylated aryl sulionate type, and which containsubstantial amounts of the said novel cyclo-alkylene-aromaticsulfonates, can be made from chlorinated hydrocarbon mixtures which arechlorinated to a much higher degree and contain large proportions ofpolychlorinated hydrocarbons. Thus my invention greatly improves theefilciency of conversion of suitable petroleum hydrocarbon fractionsinto high quality detergent products.

In accordance with the invention, the hydrocarbon mixture is chlorinatedto a degree corresponding to more than 100 per cent, and preferably notmore than 200 per cent chlorination. Within these limits it is preferredto chlorinate the hydrocarbon mixture to a degree corresponding to notmore than 1'75 per cent chlorination. Especially valuable results areobtained when the chlorination is carried out to a degree correspondingto from per cent to 150 per cent chlorination, or more specifically to adegree corresponding to about per cent chlorination. By chlorinating tofrom 110 to per cent chlorination, nearly maximum yields of high-qualityproducts are obtained, and the consumption of chlorine is kept at areasonable level.

The hydrocarbon mixtures employed in the present process are complexmixtures, such as petroleum distillates, whose compositions are notdefinitely known. The approximate composition of petroleum distillatesis determined by reference to the boiling points and the other physicalproperties of the compositions. Ordinarily, the petroleum distillatesemployed in the making of the side-chain aromatic compounds will boilover ranges, the lower boiling points of which are not below 80 C. atatmospheric pressure, and the upper boiling points of which are notabove 350 C. at 25 mm. absolute pressure. For the manufacture ofproducts designed for general detergent use it is preferred to employpetroleum fractions derived from Pennsylvania, or Mount Pleasant.Michigan, type petroleums which'fractions-boil for the most part withinthe range 180 to 300 0., and are Preferably composed predominantly ofsaturated hydrocarbons which boil within the range of 180 to 280,C. Thusthe preferred hydrocarbon mixtures are composed predominantly ofsaturated hydrocarbons, including saturated acyclic and saturatedalicyclic hydrocarbons, conasoaoae taining to 35 carbon atoms or,better, an average of to 19 carbon atoms, and especially an average of12 to 16 carbon atoms per molecule.

As above disclosed, the present invention includes compounds or a classnot heretofore known to the art. Such compounds are characterized by astructure in which two non-aromatic carbon atoms forming part of ahydrocarbon chain are linked directly to two nuclear carbon atoms of asingle aromatic nucleus. They may be prepared by condensing apolychlorinated (dior higher chlorinated) aliphatic hydrocarbon, or amixture of chlorinated hydrocarbons comprising polychlorinated aliphatichydrocarbons, with suitable aromatic compounds.

The broad scope of my invention includes compounds and mixtures ofcompounds having the eneral formula:

wherein the grouping:

RI! -i i x represents a radical derived from a dihalogenated orcycloaiiphatic hydrocarbon radicals, at least one of which is ahydrocarbon radical; X represents a direct carbon to carbon bond .or analkylene group; (Y)n represents hydrogen oi the benzene nucleus, or one,two, or three monovalent substituents, all of which need not be alike(e. g., OH, halogen, nitro, amino, aryl, or carboxyl groups, alky1groups containing not over 6 carbon atoms, alkoxy groups containing notover 6 carbon atoms, etc.) and Z represents one hydrogen of the benzenenucleus, or a sulfonate group which replaces said hydrogen and may be afree sulfonic acid group or a salt thereof (including metal, ammoniumand organic base salts) which make the compoundwater-soluble. Preferablythe said grouping- RIII IIII P unds differing among themselves chieflyby var-- ious configurations of the grouping:

RI RI! This grouping hasa wide range of configurations in those novel.products or this invention which are prepared by using petroleumfractions as sources of the grouping.

The invention will be illustrated by the following examples. It will berealized by those skilled in the art that the invention is not limitedthereto except as indicated in the appended patent claims. The parts areby weight, the temperatures are in degrees Centigrade and the pressureis atmospheric, unless otherwise indicated. For convenience, where akerosene fraction of petroleum is used in the processes disclosed in theexamples, the product obtained by chlorinating this fraction is termedkeryl chloride and the product obtained by condensing the keryl chloridewith benzene, for example, is termed keryl benzene. It will beunderstood that the specific character of the keryl chlorides and kerylbenzenes or other keryl aryl products will be dependent upon theparticular kerosene used and the manner in which the process is carriedout.

Example 1.--l000 parts of a kerosene fraction of Pennsylvania petroleumboiling over the range 186 to 291, with per cent of the distillateboiling between 200 and about 265, were filtered into a closednickel-clad vessel fitted with a nickel agitator. 0.4 part of iodine wasdissolved in the agitated kerosene fraction. Chlorine gas, filteredthrough a porous earthenware plate, was'run at the rate of about 3 partsper minute into the liquidv charge at a temperature of 55 to 60 untilthe specific gravity of the kerosene had increased from about 0.790 to0.920. This chlorination period was about 2 hours. I

1000 parts of benzene and 25 parts of anhydrous aluminum chloride werecharged into a glass flask fitted with a glass agitator. 500 parts ofthe chlorinated kerosene were then run in with agitation. during thecourse of 20 minutes. the temperature being about 30. The agitatedmixturein the flask was heated to 45 and maintained at that temperaturefor about 1 /2 hours. The reaction mass was transferred to a separatoryfunnel and tar was allowed to separate from the crude alkylated benzenefor at least two hours. The lower, tar layer was withdrawn anddiscarded.

The crude alkylated benzene contained considerable free benzene, whichwas removed by stripping the crude alkylated benzene first to 100-105 atatmospheric pressure and then in vacuo to at 30-40 mm. absolutepressure. The residual material weighing about 450 parts was distilledat 4 mm. pressure. The first distillate forming about 7 per cent of thedistilland was removed and consisted mainly of kerosene. Thedistillation was then continued, and the'distillate obtained from thatpoint until the boiling point of the distilland was 234 at 4 mm. wascollected as alkylated benzene.

parts of the resulting alkylated benzene distillate were agitated for 45minutes with 19 parts of 100 per cent sulfuric acid; the mix was allowedto settle for 15 minutes and the acid layer was withdrawn.

The acid treated alkylated benzene was then treated with 120 parts of100 per cent sulfuric acid in a glass vessel. After agitating withoutwarming for minutes, the temperature of the mixture was raised to 55 to60 and held there with continued agitation for 1 hour. The sulfonationmixture was allowed to settle for 1 hour. Three distinct layers wereformed. The middle, sulfonic acid layer was separated from the otherlayers and drowned in 500 parts of water containing 100 parts of crackedice, the drowned mass was neutralized with 50 per cent aqueous causticsoda, and dried on a rotary drum drier.

Example 2.--10,620 lbs. Pennsylvania kerosene (having a specific gravityof 0.788 at 24 and boiling range 185" to 275) were filtered throughporous stoneware into a lead lined kettle fitted with lead-coveredagitator, thermometer well and other accessories. 4.4 pounds of iodinewere dissolved in the agitated kerosene charge which was then warmed toabout 60 and maintained between 60 and 70 while chlorine gas, alsofiltered through porous stoneware, was passed into the liquid atianaverage rate of about 300 pounds per hour, until the specific gravity ofthe chlorinated kerosene was 0.918 at 24, corresponding with 115 percent monochlorination of the kerosene. The amount of chlorine requiredfor the purpose was about 4825 lbs. The final clorinated kerosenemixture weighed 12,834 lbs. The chlorinated hydrocarbon thus obtainedwas condensed in portions with benzene as follows:

A mixture of 13,272 lbs. of benzene and 332 lbs. of anhydrous aluminumchloride was agitated and 6636 lbs. of the chlorinated kerosene mixturewere added thereto over a period of three hours, during which thetemperature of the mass rose to about 35. The mixture was then heated to45" and held there for about 1 hours. Agitation was then stopped, themixture was allowed to stand for about 2 hours; thereafter the lowertarry layer was withdrawn. The upper layer was conveyed to a strippingkettle in which the liquid was stripped of low-boiling hydrocarbons,chiefly benzene, by boiling the liquid until its temperature reached 150at atmospheric pressure, then reducing the pressure in the distillingsystem to a pressure of 3 to 4 inches of mercury absolute pressure andcontinuing the boiling without further supply of heat for about onehour, until the temperature of the distilland was about 120. Thematerial left after this stripping was distilled in vacuo until about 7per cent of the charge in the, still had been removed as distillate. Theremaining distilland was distilled, and distillate therefrom wascollected separately until the boiling point of the distilland was 250at 14 mm. mercury pressure. This last distillate was chiefly kerylbenzene, the condensation prodnot of the chlorinated hydrocarbons of thekerosene fraction and the benzene.

The kerylbenzene was treated with 100 per cent sulfuric acid by mixingit with about 15 per cent of its weight of the acid and agitating themixture for about 1 hour at about 40. The mixture was allowed to standabout hour to' permit separation of the acid, which constituted thelower layer and was withdrawn.

The upper acid-treated layer of kerylbenzene was mixed withabout 1.25times its weight of 100 per cent sulfuric acid at a temperature betweenand The mixture was then warmed to 55 and agitated at that temperaturefor 1 hour. It was then allowed to stand for 2 hours during which timethree layers of material separated. The top layer was chieflyunsulfonated material; the middle layer was chiefly sulfonatedkerylbenzene; and the bottom layer was spent sulfuric acid. The middlelayer was separated from the others; drowned in ice water; neutralizedwith caustic soda (aqueous solution), and dried on a rotary drum drier.

Example 3.-Part 1.Chlorine is passed into 400 parts of a keroseneboiling from about 195 to about 300 (and boiling for the most part fromabout 225 to 275), having a specific gravity of 0.799 at 24, containingabout 5.6 per cent of unsaturated hydrocarbons, and having a probablecarbon content ranging from 11 to 18 carbon atoms and a probable averagecontent of about 13.4 carbon atoms, at 50 in diffused light until thereis an increase of weight of 111 parts, 2 parts of which are due todissolved hydrogen chloride. The resulting product comprisesunchlorinated hydrocarbon in admixture with monodiand polychlorinatedhydrocarbons, the average chlorine content of the mixture beingequivalent to about one and one-half atoms of chlorine per molecule ofhydrocarbon having the stated carbon content.

Part 2.-150 parts of the chlorinated mixture produced in Part 1 of thisexample are slowly added to an agitated mixture of 200 parts of phenoland 5 parts of anhydrous zinc chloride at 75, and the temperature ismaintained at 75 for about 30 minutes after all the chlorinated mixturehas been added. The temperature of the mixture is then raised andmaintained at 135 for 2.5 hours. 5 parts of zinc dust are then added,and after one hour another 5 parts of zinc dust are added, thetemperature being maintained during this addition, and for about 3 hoursafterward, at 135. The reaction mixture is cooled, treated with water,and the oil is separated from the water and residual zinc dust andfractionally distilled. The fraction boiling from 140 to 250 at 4 mm.pressure is separately collected. The product, which is an oil showingfluorescence under ultra-violet light, insoluble in water, soluble inalcohol, gasoline and other organic solvents, is comprised mainly of amixture of alkylated phenols.

Example 4.-10 parts of an alkylated phenol mixture obtained by a processsuch as is described 0 in Example 3 are stirred and thereto 10 parts ofsulfuric acid monohydrate (100 per cent sulfuric acid) are addedslowlyso that the temperature of the reaction mixture does not exceedabout 30 to 35. The sulfonation mixture is then warmed to 40 and held atthat tempertaure until a sampie is completely soluble in neutral. acidand alkaline water, and/or does not precipitate calcium salts from acalcium chloride solution containing the equivalent of 0.224 gramcalcium oxide per llter (30 to minutes). The solution is sometimesslightly turbid due to the presence of insoluble impurities. Thesulfonation mass is then diluted with water to about parts by weight andneutralized with sodium or potassium hydrox- 05 ide, or theirequivalents. The neutral solution of sulfonates is filtered andevaporated to dryness.

Example 5.--A mixture of alkylated cresols is prepared by condensingcrude cresylic acid with 70 the aid of zinc chloride as condensing agentwith a mixture of alkyl chlorides obtained by reacting a saturatedpetroleum distillate having a boiling range from 220 to 240 C. andcontaining an aliphatic hydrocarbon chain having about 13 to 76 14carbon atoms with chlorine until its weight has increased approximately18.5%. 100 parts by weight or this alkylated cresol mixture is agitatedrapidly while 128 parts of 100% sulfuric acid are added with temperatureoi the sulfonation mixture controlled to remain around 30 C. throughoutthe addition. The sulfonation 'mass is then warmed to 75 C. and heldthere until a sample is completely solublein water and does notprecipitate calcium salts (about 30 minutes). The sulfonation mass isthen diluted, neutralized with caustic soda, filtered and evaporated todryness.

Example 6.--The petroleum fraction used in this example is knowncommercially as white oil" and is a purified distillate or which underan absolute pressure of'lO mm. of mercury more than 98 per cent distilsover the range 157 to 278 C. and more than 85 per cent distils over therange 195 to 260 C. For convenience, the condensation products fromwhite oil and benzene are called white-oil-benzene" compounds.

2270 lbs. of white oil were agitated in a vessel lined with lead. 1.75lbs. of iodine were-dissolved in the agitated white oil. Chlorine gaswas then passed through the oil with continued agitation until thespecific gravity of the sample showed an increase of 0.09 over that orthe original white 011. During chlorination, the temperature wasadjusted to 70 to 86 C. by suitably heating or coolingl the batch. Thechlorinated white oil weighed 2651 lbs. The degree of chlorinationcorresponded to about 150% chlorination.

617 lbs. of benzene and 62 lbs. of anhydrous aluminum chloride wereagitated in an Allegheny metal kettle, warmed to 35 to 40 C, and held atthat temperature for about an hour and a quarter during which period 617lbs. of the chlorinated white oil (prepared as above described were runin. The agitated mixture was then warmed at 55 C. and agitated at 55 to59 C. for an hour. The agitation was then stopped and the batch wasallowed to settle for about 18 hours.

During this period, the batch was allowed to cool down to about 30 C.Some 248 lbs. of tar which settled out were discarded.

The crude condensation product was transferred to a stripping kettle,and unreacted benzene was stripped off by gradually heating the batch to150 C. and holding it at that temperature until distillation ceased andthen simultaneously increasing the vacuum in the still to lapproximately27 inches of mercury and gradually heating the distilland to about 175C. The remaining stripped white-oil-benzene weighed 433 lbs.

200 lbs. of stripped white-oil-benzene were charged into an enamel-linedkettle fitted with an enameled agitator and other suitable accessories.The batch was then cooled to 16 C. and 266 lbs. of 100 per cent sulfuricacid were run in during an hour and a quarter. The temperature was thenraised to 50 to 55 C. and held there for about an hour and a half. 120lbs. of water were then added slowly to the batch, which was cooled sothat the final and highest temperature thereof was 66 C. To the mixture,80 lbs. 01' Stoddard solvent were added. After agitatin the batch forminutes, and then allowing it to stand for one hour, the lower spentacid layer was drawn off, Then 80 lbs. more of Stoddard solvent wereadded to'the batch which was agitated for 15 minutes and allowed tostand for about 18 hours before the rest of the spent acid was drawnoff.

The sulfonation mixture was then neutralized with 60 per cent aqueouscaustic soda solution. The resulting product, which was a solution ofwhite-oil-benzene-sodium-sulfonate in Stoddard solvent, is adapted foruse in preparing highly efllcient detergent ompositions for drycleaning.

Example 7.A-ker0sene fraction of Pennsylvania petroleum distillatehaving a boiling range of about 172 to about 250 C., which, on the basisof its source and properties, was considered to be a mixture ofhydrocarbons (mainly openchain aliphatic hydrocanbons) having a rangefrom about 10 to about 15.5 carbon atoms per molecule, was chlorinatedin diffused daylight at a a temperature between 50 and 60 C. until about21 parts of chlorine had been absorbed per 100 parts of kerosene(corresponding to about 109 per cent chlorination). 200 parts of thismixture of chlorinated hydrocarbons were reacted at ordinary temperaturewith 150 parts of monochlorbenzene and 20 parts of anhydrous aluminumchloride. The temperature of the mixture was allowed to rise to about 60C. with agitation and this agitation was continued for about oneadditional hour after this temperature was reached. The mixture wasallowed to stand and separate into two layers of which the upper wasdecanted, washed with dilute hydrochloric acid and distilled until avapor temperature of 120 C. at 5 mm. was reached. The residue parts) wasan amber-colored oil comprising chiefly a mixture of alkylatedchlorbenzenes in which the hydrocarbon groups introduced by alkylationcontained from about 10 to 15.5 carbon atoms. 20 parts of the oil weresulfonated by mixing it with 25% parts of 26 B. oleum at a temperaturefrom about 10 to 15 C. for about 3 hours. The mixture was then heated to40 to 55 C., where it was held for about one-half hour. The mixture wasthen diluted by drowning it in 6 to 7 times its weight of ice and water,neutralized with concentrated aqueous caustic soda and dried. Theresulting product was an almost white solid soluble in water toformsubstantially colorless solutions having desirable wetting andwashing properties. The product was chiefly a mixture of nuclearlyalkylated chlorbenzenes in which the hydrocarbon groups introduced byalkylation contained from about 10 to about 15.5 canbon atoms.

Example 8.-Part 1.Chlorine was passed into a kerosene (a purifiedPennsylvania petroleum distillate) which boiled from 245 to 315 C., and.of which per cent distilled between 260 and 305 C., and had a specificgravity of 0.815, contained in a closed, lead-lined vessel which wasequipped with a vent for hydrogen chloride produced by the chlorination.The chlorination was carried out in the dark, but to facilitate thechlorination the kerosene initially contained about 0.45 part of iodineper 1000 parts of kerosene. The temperature of the reaction mass waspreferably maintained at about 45 to 50 C. The introduction of chlorinewas continued until the weight of the mass increased to an extent whichcorresponded substantially with per cent chlorination. The specificgravity of the reaction mixture reached about 0.915.

Part 2.--300 parts of the above chlorinated kerosene were mixed with 30parts of anhydrous aluminum chloride and parts of commercial diphenyl.The mixture was agitated under reflux at room temperature (that is, atabout 15 to 30 C.) for about one hour and thereafter at about 75 C. forabout one and a half hours. The mass was then cooled to about 20 to 30C. and poured into a mixture of 600 parts of ice water and 30 parts ofcommercial muriatic acid. The aluminum salts dissolved in the 'colddilute acid while the organic matter, which contained the alkylateddiphenyl compounds, was precipitated in a semi-liquid, pasty form. Smallamounts of benzene and/or ether were added to the agitated aqueousmixture to dissolve the organic products. Upon standing, the mixtureseparated into an upper layer which was a solution of the organic matterin the organic solvent, and a lower aqueous acid layer which waswithdrawn and discarded. The benzol and/or ether solution of organicmatter was washed with water until it was reasonably free of acid, andwas then distilled in vacuo. The fraction of the distillate which boiledat about 170 to about 260 C. at

mm. pressure was collected separately. It was a light-yellow viscous oilwhich was insoluble in water, but soluble in benzene and in ether. Itwas a mixture comprised chiefly of alkylated diphenyl compounds in whichthe hydrocarbon groups introduced by alkylation corresponded with thekerosene hydrocarbons employed. It also contained some chlor-alkyldiphenyl compounds derived from the dichlor hydrocarbons.

Part 3.-25 parts of the oil obtained according to Part 2 of this examplewere mixed with 15 parts of 100 per cent sulfuric acid and stirred atabout 90 C. for about 20 minutes, or until a 1 cc. sample waspractically completely soluble in about cos. of water at about 25 C. Thesulfonation mass was poured into 300 parts of water and the aqueous acidmixture was neutralized with caustic alkali or a water-soluble carbonate(e. g., sodium carbonate) and the resulting neutral solution was dried.The product was chiefly a mixture of the salts (e. alkali metal salts)of alkylated-diphenyl sulfonic acids. It was a light-brown to whitesolid which was soluble in water, and in aqueous solutions of mineralacids and of water-soluble alkalies.

- Example 9.Part A.--To an agitated mixture mixture of 1000 grams ofcommercial lauryl alcohol and-60 grams Supercel (commercial diatomaceousearth), 225 grams of phosphorus pentoxide were added in small portionsduring the course of about 1% hours. Considerable heat was evolved.After adding the last portion of phosphorus pentoxide, the mixture wasagitated for 3 hours longer. The reaction mass was allowed to settle andthe liquid portion decanted from the phosphoric acid sludge. The crudeproduct was distilled under an absolute pressure of about 10millimeters. The product was redistilled at atmospheric pressure. Thefraction boiling between 214 and 220 was collected as the desiredproduct, and was chiefly dodecene.

Part B.A charge of 1100 grams of dodecene, prepared in Part A above,while being agitated, was warmed to 49 to 51 and into the warm agitatedmaterial, a stream of chlorine vapor was passed at the rate of about 2grams per minute. After three hours and twenty minutes, the gain inweight of the chlorinated mixture was 363 rams. The chlorination wascontinued for an additional 53 minutes; then a current of air was passedthrough the chlorinated hydrocarbons for 10 minutes to remove dissolvedchlorine and hydrogen chloride. The gain in weight of the hydrocarbonwas 465 grams.

The chlorinated hydrocarbon was twice carefully fractionated at 1.5 to 4mm. mercury absolute pressure, using a Vigreux column. The fractioncollected as dodecene dichloride had a boiling range of about to at 2mm. mercury absolute pressure.

Part C'..A mixture of 51.3 grams of granular anhydrous aluminum chlorideand 2050 grams of benzene were agitated at room temperature. Then 613grams of dodecene dichloride prepared in Part B above were run in as asteady stream during the course of about 30 minutes. The temperature wasthen raised to 44 to 46 and agitation continued for 1 hour. Thetemperature was then allowed to fall to room temperature and the mixtureagitated for about 16 hours longer. The condensation reaction mixturewas decanted from the solid aluminum chloride residue.

The condensation reaction mixture was distilled. Unreacted benzene wasremoved by distilling flrst at atmospheric pressure and then at 40 mm.mercury absolute pressure until the vapor temperature was 80. Theresidual distillant was then subjected to repeated fractionaldistillation. Two main fractions were isolated. One of these, fractionA, boiled at 154 to 171 at 4 mm. and weighed 221 grams. The other,fraction B, boiled at 203 to 220 (at 4 mm.) and weighed 154 grams.Fraction A was largely a mixture of alkylated benzenes in which thehydrocarbon groups introduced by alkylation contained 12 carbon atoms ina chain and two of the carbon atoms of a chain were directly linked totwo adjacent carbon atoms of the benzene nucleus to form a cycliccompound having a formula of the type formula set out above, hereintermed for convenience cyclododecylene benzenes. Fraction 3, on theother hand, was largely di(phenyl) laurane.

Part D.100 grams of fraction A (see Part C oi! this example) were mixedwith grams of 100% sulfuric acid at a temperature between 30 and 35. Themixture was then warmed to 55 and agitated at that temperature for 1hour. It was then allowed to stand 'for 2 hours during which time twolayers formed. The lower layer was spent sulfuric acid. It was drawn offand discarded. The upper layer was chiefly sulfonated cyclododecylenebenzenes" which was drowned in ice water, neutralized with aqueouscaustic soda (50%) and dried on a rotary double drum drier. The drumshad an external diamete of 6 inches and were chromium plated. They wererotated at a speed of 3 to 4 revolutions per minute and were heatedinternally to a temperature of about 150 C. by steam under about 60 lbs.gauge pressure. The flaky, light-colored product had excellent detergentproperties.

Example 10.-Part A.A large batch of Pennsylvania kerosene (boiling rangeto 266 with over 80% boiling between 200 and 260) was fractionallydistilled, and-the various fractions having similar boiling ranges werecombined and refractionated. Finally two fractions were isolated, No. 1from 245 to 250, and No. 2, boiling from 250 to 255, both at atmosphericpressure.

Each fraction was warmed-to 50, agitated in a glass flask andchlorinated by passing in chlorine vapor until the gains in weightcorresponded, respectively, to 100% (for No. 1) and 108% (for No. 2) ofthe gain in weight theoretically required for conversion of thehydrocarbons coma for about 25 minutes.

using the same procedure as before. The chlorinated fractions from No. 1were then redistilled several times and fractions boiling as followswere isolated:

Up to 153 at mm 50 s. (unchlorinated hydrocarbons) II. 153 to 163 at 20mm 153 g. (monochlorinated hydrocarbons) III. .Above 163 at 20 mm 146 g.(polychlorinated hydrocarbons) Fraction 11 thus obtained was thekerosene used in Part B of this example- The mixture obtained onchlorinating fraction No. 2 (boiling range 250 to 255) was fractionallydistilled several times, and the fraction boiling above 163 at 20 mm. ofmercury absolute pressure was collected. This was combined with the 146grams of polychlorinated hydrocarbon material obtained from No. 1, andthe resulting mixture fractionally distilled. A fraction boiling from175 to 185 at 20 mm. of mercury was the dichlorinated kerosene used inPart B of this example. The fraction boiling above 185 at 20 mm. ofmercury was the higher polychlorinated kerosene used in Part B of thisexample.

Port B.The above-described mono-, diand higher polychlorinated kerosenes(designated keryl chlorides) were condensed with phenol using anhydrouszinc chloride as catalyst. The

details of these condensation experiments are given in the followingsummary:

minutes, the chlorine stream was discontinued and a current of air waspassed through the chlorinated hydrocarbon mixture for 5 minutes toremove-uncombined dissolved chlorine. The gain in weight due toorganically combined chlorine was 308 grams. The specific gravity of thechlorinated hydrocarbon was 1.0216 at 24.

791 grams of chlorinated hydrocarbon material prepared as describedabove were distilled using a one-foot column filled with Berl saddles.Fractional distillation was carried out at atmospheric pressure toeflect separation of the lowboiling material (caprylene and octylchloride) and at a pressure of 30 mm. of mercury to isolate thecaprylene dichloride fraction which boiled within the range 192 atatmospheric pressure to 120 at 30 mm. A two-foot glass column filledwith Berl saddles was then used in insuring complete removal of materialboiling below 100 at 30 mm.

Part B.--1735 grams of benzene and 43.3 grams of granular anhydrousaluminum chloride were agitated and 400 grams of caprylene dichloride(prepared as described above) were. run in as .a slow stream during thecourse of half an hour.

The reaction mixture was then warmed to during the course of 5 minutesand agitated at 44 to 46 for 1 hour, and then at about 24 for about 16hours. The reaction mixture was then allowed to stand for about 2 hours.Tar which separated out was discarded. The crude reaction product wasthen fractionally distilled, first at atmos- Runl Run II Run III Amixture consisting of....

The crude washed product was then iractionally distilled under anabsolute pressure of.

Three fractions were collected in {140*175'" 18 each case. These three,fractlons were combined Ya purified keryl phenol product.

(1 Yield per 100 g. of kerylchloride 4 mm. mercury 150 g. kerylmonochloride, 150 g. phenol, 130 g. zinc chloride.

g. keryl dichloride, 100 g.

g. keryl higher polychloridc, phenol, 75 g. zinc chloride.

300 g. phenol, 25 g. zinc chloride. 20 minutes 20 minutes.

4 hours at reflux temperature 4 mm. mercury 3 hours at refluxtemperature.

3 mm. mercury.

pie-175, 6 g 160-175, 3 g.

Each of the three purified keryl phenol'products was sulfonated asfollows: 25 grams of keryl phenol product were stirred in a glass flask.17

cc. of sulfuric! acid were run in during about 15 minutes at roomtemperature. The mixture was then warmed to 80 and agitated Thesulfonation mixture was diluted with about 250 cc. of cold water andneutralized with 50% aqueous caustic soda. The neutralized solution wasdried on a double drum drier.

The dried products were tested for detergency and scouring power. Theresults showed that as detergents, the mixture of sulfonates made fromthe keryl dichloride was definitely superior to the mixtures ofsulfonates made from the keryl monochloride' and from the keryl higherpolychloride and the mixture of sulfonates made from the keryl higherpolychlorides was equal to the mixture made from the keryl monochloride.

Example 11.--Part A.490 grams of caprylene (having a specific gravity of0.7204 at 24 and refractive index N of 1.4160) were agitated in a glassflask and treated at 39 to 41 with a stream of chlorine flowing at arate of about 3 grams per minute. After chlorinating for 104 .phericpressure to remove excess benzene and then at reduced pressure (30 to 10mm. of mercury absolute pressure) to efiect separation of thecondensation products. Five fractions were collected at the followingtemperatures and pressures:

1. at 30 mm. to at 20 mm. 2. 130 to at 20 mm. 3. 145 at 20 mm. to 140 at10 mm. 4. 140 to at 10 mm. 5. 150 at 10 mm. to at 5 mm.

soda. The neutralized solution was dried on a rotary drum drier. Theflaky, light-colored product was a good wetting agent in aqueoussolution.

'It is noted that the products obtained in the I above examples allcomprise hydrocarbon-substituted aromatic compounds of the peculiarstructure above mentioned; namely, a hydrocarbon-substituted aromaticcompound having at least 7 carbon atoms in a hydrocarbon radicalintroduced by alkylation, of which radical two non-aromatic carbonsatoms are linked directly to two adjacent carbon atoms of the aromaticnucleus. Further, as is evident from the above examples,hydrocarbon-substituted aromatic sulfonate mixtures which contain anaromatic nucleus doubly linked at adjacent carbon atoms of the nucleusto an aliphatic hydrocarbon radical together with alkylated aromaticsulfonates linked at a single carbon atom of the aromatic nucleus to asingle carbon atom of an aliphatic hydrocarbon radical, constitutevaluable detergent mixtures.

It will be evident to those skilled in the art that the invention is notlimited to the details of the foregoing illustrative examples and thatchanges can be made without departing from the scope of the invention.

Catalysts may be used to speed up the rate of chlorination. For example,iodine .may be added to the hydrocarbon mixture, or phosphoroustrichloride vapors may be added to either the chlorine gas or thehydrocarbon mixture. Or, the reacting materials may be exposed tochemically active radiations, e. g., actinic rays, such as sunlight.Although the use of catalysts may frequently be helpful in acceleratingthe reaction, the scope of this invention is not limited to chlorinationprocesses in which catalysts are used,

The invention furthermore is not limited to treatment of the aromaticcompounds disclosed in the above examples but may be employed inconnection with the manufacture of other'hydrocarbon-substitutedaromatic compounds and especially those of mononuclear aromatichydrocarbons and their simple unsulfonated substitution products.Examples of such compounds are benzene, toluene, diphenyl, phenol,cresol, anisole, phenetole and salicylic acid. Benzene is preferred.

In carrying out the condensation process between the halogenatedhydrocarbon material and the aromatic materials, it is necessary toselect the aromatic material so that two ortho carbon atoms of the ringor nucleus may become attached to two carbon atoms of the aliphatichydrocarbon radical, i. e., so that said carbon atoms are susceptible toalkylation.

The yield of desirable alkylated aromatic sulfonates is greatlyinfluenced by the proportion of chlorinated petroleum fraction employedwith respect to the amount of aromatic hydrocarbon or unsulfonatedderivative thereof used in the preparation of the alkaylated aromaticcompounds. Theoretically, in order to obtain complete reaction one molof aromatic compound must be used per atom of chlorine combined with thepetroleum hydrocarbon fraction. In practice an amount of aromaticcompound in large molecular excess, preferably about twice the weight ofchlorinated petroleum is used, as this favors complete reaction of thechlorinated petroleum with the aromatic body, and permits lessdecomposition and undesirable by-products in the condensation reaction.

The improved results of the present invention are best effected by acondensation of the chlorinated hydrocarbon and aromatic compound withan amount of anhydrous aluminum chloride which is from 1 to 8 per centof the weight of chlorinated hydrocarbon charge; a better and preferableproportion is from 2 per cent to 5 aaoacao per cent. In general, withamounts less than 2 per cent, condensation is retarded, while withamounts larger than 5 per cent there is no marked increase in the rateof condensation and the yield is somewhat decreased, though the qualityof condensed product is improved.

The particular manner in which the sulfonation is carried out forms nopart of the present invention; this step can be carried out in any suitable manner. For example, sulfuric acids of various strengths such as 66B. sulfuric acid, 100 per cent sulfuric acid, 26 cent oleum and 65 percent oleum, and chlor-sulfonic acid may be used as sulfonating agents.The sulfonation may be carried out in the presence of inert solvents ordiluents, and sulfonation assistants as, for example, the lower fattyacids and their anhydrides, such as acetic acid and acetic anhydride, orthe alkali metal sulfates, such as sodium or potassium sulfate, may beemployed. Also, the temperature at which the sulfonation is carried outmay vary within wide limits. For example, temperatures as low as about 0C. and as high as about 140 C. maybe employed. In general, the morevigorous thesulfonating agent the lower is the preferred temperature. Inmost cases the sulfonation is carried out most emciently at temperaturesbetween 5 and C. For complete sulfonation the sulfonating agent in termsof per cent sulfuric acid may be employed in amounts which range from0.3 to 5 times or more the weight of the condensation product to besulfonated. Ordinarily, the extent to which the sulfonation is carriedout will vary with the individual material being sulfonated, the

duration of the sulfonation, and the use to be made of the sulfonatedproduct. Monosulfonation is preferred.

- The hydrocarbon-substituted aromatic sulfonates may be prepared in theform of-their free sulfonic acids or in the form of their salts. Thusthey may be prepared in the form of their alkali metal, alkaline earthmetal, ammonium, or organic base salts (e. g., amine salts). They are ofparticular value in the form of their alkali metal and especially sodiumsalts.

The temperature of chlorination of the hydrocarbon mixtures may bevaried. Thus, temperatures as low as 0 C. or as high as 200 C. may beemployed. I have found that it is advantageous to carry out thechlorination of the hydrocarbon mixture, such as a kerosene or white oilfraction of petroleum, for the most part, and

preferably for substantially the entire chlorination period, at atemperature which is above 40 C., and preferably between 60 C. and 200C. For the chlorination of kerosene fractions of petroleum distillates,chlorination temperatures of about 60 to C. are employed with advantage.The optimum chlorination temperature varies with the hydrocarbon mixturebeing chlorinated. In general, the higher boiling mixtures, such aswhite oil, ar chlorinated efficiently in the neighborhood of 80 C.

Preferably, as practiced in the processes of the above examples, theproducts resulting from the condensation-of mixtures of chlorinatedhydrocarbons with aromatic compounds are distilled, preferably undervacuum conditions, to concentrate the desired cyclo-alkylene-aromaticcompounds and to separate them from higher boiling compounds such aspoly (phenyl) alkanes, and lower boiling compounds such as lower boilingalkanes.

This application is a continuation-in-part of asaasae my applicationsSerial No. 691,082, filed September 26, 1933, now U. S. P. 2,249,757,issued July .22, 1941; Serial No. 257,720, filed February 21, 1939, nowU. S. P. 2,267,725, issued December 30,

U. S. P. 2,223,364, issued December 3, 1940.

I Since changes may be made in the process described above withoutdeparting from the scope of the invention it will be understood that thedescription should be interpreted as illustrative and not in a limitingsense.

I claim:

1. A detergent mixture. of hydrocarbon-substituted aromatic sulionateshaving at least 7 carbon atoms and an average of 10 to 19 carbon atomsin hydrocarbon radicals introduced by alkylation, in which the saidradicals are derived from an aliphatic hydrocarbon mixture of the typeof petroleum distillate containing an average of 10 to 19 carbon atomsper molecule,

said detergent mixture including hydrocarbon substituted aromaticsulfonates in which a single non-aromatic carbon atom of a hydrocarbonradical introduced by alkylation is linked directly to a carbon atom ofthe aromatic nucleus and hydrocarbon-substituted aromatic sulfonates inwhich two'non-aromatic carbon atoms of a hydrocarbon radical introducedby alkylation are linked directly to two adjacent carbon atoms of thearomatic nucleus, said detergent mixture being obtained by chlorinatingthe hydrocarbon mixture to a degree corresponding with more than percent and not more than 200 per cent chlorination, condensing theresulting mixture of chlorinated hydrocarbons with an aromatic compoundhaving a pair of ortho nuclear carbon atoms susceptible to alkylation,and sulfonating the resulting mixture of hydrocarbon-substitutedaromatic compounds.

2. A detergent mixture of hydrocarbon-substituted aromatic sulfonateshaving at least 7 carbon atoms and an average of at least 10 carbonatoms in hydrocarbon radicals introduced by alkylation, in which thesaid radicals are derived from a hydrocarbon mixture of the type of apetroleum distillate containing an average of 9 alkylation, in which thesaid radicals are derived irom a paramnic petroleum distillatecontaining an average of 10 to 19 carbon atoms per molecule, saiddetergent mixture including hydrocarbon-substituted aromatic sulionatesin which a single non-aromatic carbon atom oi a hydrocarbon radicalintroduced by alkylation is linked directly to a carbon atom of thearomatic nucleus and hydrocarbon-substituted aromatic sulionat'es inwhich two non-aromatic canbon atoms of a hydrocarbon radical introducedby alkylation are linked directly to two adjacent carbon atoms oi thearomatic nucleus, said detergent mixture being obtained by chlorinatingthe petroleum distillate to a degree corresponding withmore than percent chlorination and not more than 200 per cent chlorination,condensing the resulting mixture or chlorinated hydrocanbons with anaromatic compound having a pair oi ortho nuclear carbon atomssusceptible to alkylation, and suli'onating the resulting mixture oihydrocarbon-substituted aromatic compounds.

- 4. A detergent mixture of hydrocarbon-substituted benzene sulionateshaving at least 7 carbon atoms and an average of 10 to 19 carbon atomsin hydrocarbon radicals introduced by alkylation, in which the saidradicals are derived from a hydrocarbon mixture of'the type of petroleumdistillate containing an average of 10 to 19 carbon atoms per molecule,said mixture including hydrocarbon-substituted benzene sulfonates inwhich a single non-aromatic carbon atom of a hydrocarbon radicalintroduced by alkylation is linked directly to a carbon atom of thebenzene nucleus and hydrocarbon-substituted benzene sulfonates in whichtwo non-aromatic carbon atoms of a hydrocarbon radical introduced byalkylation are linked directly to two adjacent carbon atoms 01 thebenzene nucleus, said detergent mixture being obtained by chlorinatingthe hydrocarbon mixture to a degree corresponding with more than 100 percent chlorination, condensing the resulting mixture oi chlorinatedhydrocarbons with benzene, and sulfonating the resulting mixture ofhydrocarbon-substituted 'benzenes.

5. A detergent mixture of hydrocarbon-substituted aromatic sulfonates inwhich hydrocarbon radicals introduced by alkylation are derived from thehydrocarbon constituents of a petroleum fraction boiling within therange to 300 C. at atmospheric pressure, said mixture includinghydrocarbon-substituted aromatic sulfonates in which a singlenon-aromatic carbon atom of a hydrocarbon radical introduced by'alkylation is linked directly to a carbon atom of the aromatic nucleusand hydrocarbon substituted aromatic tained by chlorinating thehydrocarbon mixture to a degree corresponding with more than 100 percent chlorination, condensing the resulting mixture of chlorinatedhydrocarbons with an aromatic compound having a pair of ortho nuclearcarbon atoms susceptible to alkylation, and sulfonatlng the resultingmixture oi hydrocarbon-substituted aromatic compounds.

3. A detergent mixture of hydrocarbon-substituted aromatic sulfonateshaving at least 7 carbon atoms and an average of 10 to 19 carbon atomsin hydrocarbonradicals introduced by sulfonates in which twonon-aromatic carbon atoms of a hydrocarbon radical introduced byalkylation are linked directly to two adjacent carbon atoms of thearomatic nucleus, said mixture being obtained by chlorinating thepetroleum fraction to a degree corresponding with more than 100 per centchlorination and not more than 200 per cent chlorination, condensing theresulting mixture of chlorinated hydrocarbons with an aromatic compoundhaving a pair of ortho nu- 10 2,sas,sae

petroleum fraction boiling within the range 180 to 300' C. atatmospheric pressure, said mixture including hydrocarbon-substitutedbenzene sulfonates in which a single non-aromatic carbon atom of ahydrocarbon radical introduced by 5 alkylation is linked directly toacarbon atom of the benzene nucleus and hydrocarbon-substitut-ed benzenesulfonates in which two non-aromatic carbon atoms of a hydrocarbonradical introduced by alkylation are linked directly to two 10 LAWRENCEH. F'LE'I'I'.

